Omega-cyanoperfluoroalkanoyl chlorides



United States Patent "ice Meme, 321 1 23 are reacted with a compound selected from the group con- 3,349,105 sisting of w-CYANGPERFLUOROALKANOYL CHLORIDES Carl J. Verbanic, Louisville, Ky., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York and No Drawing. Filed Aug. 18, 1966, Ser. No. 573,195 4 Claims. (Cl. 260404) in the presence of a Lewis acid catalyst, where x is as defined above. A more preferred range for X is from 2 to w-Cyanoperfluoroalkanoyl chlorides of the formula compqunds embraced y this invention are:

a-cyanodifluoroacetyl chlor1de, ON w-cyanotetrafluoropropionyl chloride,

/ w-cyanohexafluorobutyrl chloride,

w-cyanooctafluorovaleroyl chloride,

w-cyanodecafluorohexanoyl chloride,

w-cyanododecafluoroheptanoyl chloride, w-cyanotetradecafiuorooctanoyl chloride, wherein x is from 1 to 12 are formed when perfluorinated wcyanohexadecafluorononanoyl chloride,

amides of the formula w-cyanooctadecafiuorodecanoyl chloride,

0 w-cyanoeicosafluoroundecanoyl chloride, and lg NH w-cyanodocosafluorolauroyl chloride.

By this process, at the same time the corresponding di- (C nitrile is also prepared, which under some conditions yields CNH2 greater than 55 percent of the theoretical even without 0 sophisticated equipment and reaction modifications. This I is illustrated in Examples l-lO below, wherein temperaare reacted with a compound selected from the group tures are in degrees centigrade and parts are by weight. consisting of C01 CO];

Example 1 25 grams (0.105 mole) of perfluoroglutaramide were added to 61 grains (0.312 mole) of benzotrichloride and and 0.8 gram of zinc chloride (1 weight percent). The mixture was heated to 180 degrees centigrade. The nitrile was C013 collected in a Dry-Ice trap. After warming to room temperature to boil off the HCl gas, the residue was distilled in the presence of a Lewis acid catalyst, Where x is as deto give a product having a boiling point of 38 degrees fined above. These new compositions are important intercentigrade. Infrared analysis showed the presence of the mediates in the preparation of perfluorinated diamidine 40 CEN bond and no C O bond. elastomers as well as other useful plastics. The equation for the reaction of Example 1 is:

i 0013 This is a continuation-in-part of United States Ser. No. 811,813, filed May 8, 1959, now abandoned, and Ser. No. Zn012 288,464, filed June 17, 1963, now U.S. 3,274,229.

This invention relates to new compositions of matter ll classified as w-cyanoperfluoroalkanoyl chlorides. These compositions are Simultaneously p p when perfiuorigiiiiii fiide giill ii e iiiignae Elfiillfiliinn nated amides, such as perfiuoroglutararnide, perfluorosuccinoamide and perfluoroadipoamide, are dehydrated to 6 perfluoroglutaronitrile, perfluorosuccinonitrile and per- 001 /CC1 gllgiogglgilinle, in accordance with the teaching of on (on) H01 In accordance with the present invention, w-cyanoper- ("301 ON fiuoroalkanoyl cholrides of formula 0 perfluorow-cyano- CN glutarylperfiuorochloride butyryl (on) x chloride Instead of zinc chloride, suitable proportions, e.g., 0.2-5

(n) percent by weight of the reactants of other Lewis acid catalysts such as aluminum and ferric chlorides and other known Lewis acid metallic chlorides may be substituted wherein x is from 1 to 12 are formed when perfluorinated for the Zinc chloride with Similar good results amides of the formula 0 this invention. ll Example 2 a, Into a one liter, three-necked flask were placed 400 O NHZ milliliters of trichlorobenzene and 244 grams (1.25 moles) benzotrichloride and 4 grams ZnCl The flask was fitted O with a mechanical stirrer, Vigreux column with distilling Example 2 illustrates another dehydration method of.

head, thermometer and dripping funnel. The solvent and benzotrichloride were heated to 170 degrees centigrade and the slow addition of a trichlorobenzene slurry of 100 grams (0.42 mole) of perfluoroglutaramide started. The addition took 2.5 hours. The exit gases were cooled by a spiral condenser off the distilling head and cooled in a wet ice trap followed by a series of Dry-Ice traps. The perfiuoroglutaronitrile was collected in the Dry-Ice traps. After addition of all the amide the temperature was raised to 195 degrees centigrade, and a fraction collected which boiled at 110' degrees centigrade. After distillation of the products there were obtained 35 gramsof perfluoroglutaronitrile (41.3 percent) and 27 grams of perfluoroglutaryl chloride, boiling point 110 degrees centigrade (23.1 percent). Instead of benzotrichloride, xylene hexachloride may be used with similar results. This is also the case when perfluorosuccinamide and perfiuoroadipamide are the starting materials.

The perfluorinated nitIiles are important intermediates in the preparation of perfiuorinated diamidine elastomers as well as other useful plastics. Copolymers of perfiuorinated diamidines and monoamidines give thermally stable fluids and elastomeric materials. Similarly, the w-cyanoperfluoroalkanoyl chlorides of the present invention ,are useful intermediates in the preparation of perfluoroalkylenetriazine polymers, such as those disclosed in copending application Ser. No 533,430, filed Mar. 11, 1966.'These polymers are thermally stable and resistant to some solvents, while being soluble in other solvents, such as alkyl acetates, alkyl perfiuoroalkanoates, and fluorinated solvents,.such as fluorinated xylenes and fluorine-containing triazines.

One of the problems in preparing perfluorinated nitriles, such as perfluoroglutaronitrile, is that, with most dehydrating agents, the perfluorinated amides cyclize on dehydration, giving greater yields of the cyclic imides such as perfluoroglutarimide than of the dinitriles. Also, by-products, including w-cyano perfluoro butyryl chloride and perfiuoroglutarylchloride, are obtained unless the mole ratio of the dehydrating agent to the starting amide is carefully controlled.

A clearer understanding of these problems will be evident-after a consideration of the following table, in which are described the reagents employed and products ob- Example 10 indicates the total unsuitability for use of several dehydrating agents, typified by benzoyl chloride.-

Although benzoyl chloride itself is not suitable, it is made as a by-product in thepresent process from benzotrichloride. Thus, it is present and is available as a useful product of the reaction and does not prevent the production af the dinitrile in the present processes. Other reagents which were tested and found unsatisfactory for use are thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and acetic anhydride.

The dehydration reactions are best carried out in the presence of metallic chloride catalysts. Typical of such catalysts which may be used are the halides of zinc, aluminum, iron, boron and tin, such as zinc chloride, aluminum chloride, ferric chloride, stannic chloride and boron trifiuoride.

The reaction temperaturesemployed will generally be between about one hundred and sixty degrees Centigrade and two hundred and ten degress centigrade and will preferably be between one hundred and ninety degrees centigrade and two hundred and ten degrees Centigrade when using benzotrichloride., When using xylene hexa-.

chloride, the reaction temperature employed will generally be between about one hundred and sixty degrees centigrade and two hundred and fifty degrees centigrade and preferably between about one hundred and ninety degrees Centigrade and two hundred and ten degrees Centigrade. The reaction may be carried out in the presence or absence of inert solvents, such as dichlorobenzene or trichlorobenzene.

Molar ratios of benzotrichloride to the starting amide may be varied considerably. However, in order to sup press formation-of by-products, mole ratios. greater than 3:1 arerequired, even when utilizing recycle to raise the yields of dinitriles.

Although ratios of 4:1 to 20:1 maybe used, some:

times with recycle, the preferred mole ratios of benzotrichloride to. the starting amide are between about 10:1 and about :1, to obtain vbest yields of the dinitrile without much imide or diacid chloride. The molar ratios of xylene hexachloride to the starting amide may alsobe varied considerably, the molar ratios required being generally one-half those required when using benzotrichloride. This is because of the two trichloromethyl groups in tained when following procedures like those of Examples 45 this compound.

1 and 2. As was mentioned previously, yields can be increased DEHYDRATION OF PERFLUOROGLUTARAMIDE Mole ratio of dehy- Perfiuoroglu- Example Dehydrating reagent drating agent Nitrile yield, Imide yield, taryl chloride Total yield,

to the perfiupercent percent yield, percnet oroglutarepercent mide 3 a Benzotrichloride 1:1 5. 2 68. 3 4.. d0 2:1 5.0 55.0 5 do 3:1 29. 6 73. 0 6 .(l0 4:1 33. 7 67. 5 7 .d0 10:1 3.0 61. 0 8,..- lo 20:1 6 .1 9 Xylene hexachloride 5:1 3.5 64.1 10 Benzoyl chloride 3:1 60.0

n The yields of dinitrile are further increased, to over in Example 3, by iractionally separating the imide from the dinitrile and treating it with ammonia to produce the diarm'de which is mixed with feed diamide and is converted to the dinitrile.

b The yields of dinitrile are further increased, to over 55% in Examples 5 and 6, as well as in Examples 1 and 2, by reacting the diacid chloride with ethanol at normal esterfication temperatures and then converting the diester to the diamide by treatment with ammonia to produce the diamide which is mixed with the feed diamide and is converted to the dinitrile.

It will be apparent from a consideration of the foregoing chart, that in Examples 3 and 4, the imide and chloride by-products are both'produced; that in Examples 5 and .6, the imide is not obtained, but the yield of chloride becomes much greater and that in Example 7, the chloride yield is low and the nitrile yield is high. Example 9 cmploying xylene hexachloridc, indicates that not as great a molar quantity of this dehydrating agent is required to by reacting by-product diacid chloride material with lower alcohols, e.g., of 1 to 4 carbon atoms, to form esters, which are then ammoniated to diamides. Usually about molar equivalent proportions of alcohol and diacid chloride will be reacted and ammonia will be in excess, e.g., 1.1 to 10 molar equivalent ratio. Although the imide may be converted to the amide, too, its separation and reaction are more difficult and such procedure is less prereach an optimum nitrile yield as with benzotrichloride. ferred.

Example 11.w-Cyanperflu0r0butyryl chloride To a mixture of 5865 parts of benzotrichloride, 87.5 parts of zinc chloride heated and stirred at 205-210 degrees centigrade in a flask equipped with a distillation column and with cold traps to collect products are added a slurry of 1190 parts of periluoroglutaramide in 1460 parts of trichlorobenzene in 4 hours. Hydrogen chloride passed through the column and traps at temperatures of zero degrees Centigrade and minus 78 degrees Centigrade leaving condensable perfluoroglutaronitrile and higher boiling liquids. The crude products were then fractionated from phosphorus pentoxide through a fractionating column giving 80 parts of w-cyanobutyryl chloride (NC(CF COCl) boiling range 74 to 75.5 degrees centigrade. The infrared spectrum was characteristic for nitrile and acid chloride with bands at 2250 and 1800 reciprocal centimeters respectively.

Analysis.-Calculated for C ClF NO: C, 25.07; Cl, 14.80; N, 5.85. Found: C, 25.15; H, 0.00; N, 5.58; Cl, 14.40.

Example 12.w-Cyan00ctafluorovaleroyl chloride In a manner after Example 11, when 1440 parts of perfluoroadipamide are substituted for perfluoroglutaramide, w-cyanooctafluorovaleroyl chloride will be produced.

Example 13.w-Cyrmoperfluorononanoyl chloride In a manner after Example 11, when 2440 parts of perfluorosebacamide are substituted for perfluoroglutaramide, w=cyanoperfluorononanoyl chloride will be produced.

Example 14 shows the preparation of w-cyanoperfluorononanoyl chloride by a method different from that of Example 11. This method was not discovered by me.

Trichloromethyl w-cyanoperfluorononanoate, (25.1 grams), and ferric chloride, (3 grams) were heated in a distilling apparatus to degrees centigrade in 2 hours, then to degrees centigrade in 1.5 hours. Vacuum (52 millimeters mercury) was then applied and the distillate was collected: Cut 1, 15.6 grams, boiling point 99-102 degrees centigrade, 89.5 percent pure by gas liquid chromatographic analysis. Cut 2, 3.0 grams, boiling point 102-110 degrees centigrade, 92.2 percent pure by gas liquid chromatographic analysis.

Analysis.-Calculated for C Cl NO: C, 24.53; F, 62.10; N, 2.86. Found: C, 24.72; H, 0.00; N, 3.10.

The infrared spectrum, was characteristics for nitrile and acid chloride with bands at 2250 and 1800 reciprocal centimeters, respectively.

Although this invention has been illustrated by citing specific details of given species embraced within the scope of the invention, it is to be understood that various modifications within the invention are possible, some of which have been referred to above.

I claim:

1. w-Cyanoperflnoroalkanoyl chlorides of the formula wherein x is from 1 to 12.

2. The compound of claim 1, wherein x is 3. 3. The compound of claim 1, wherein x is 4. 4. The compound of claim 1, wherein x is 8.

References Cited UNITED STATES PATENTS 3,274,229 9/ 1966 Verbanic 260465.2

CHARLES B. PARKER, Primary Examiner.

JOSEPH P. BRUST, Examiner. 

1. W-CYANOPERFLUOROALKANOYL CHLORIDES OF THE FORMULA 